Acetylenic diol ethylene oxide/propylene oxide adducts and processes for their manufacture

ABSTRACT

This invention provides water-based compositions, particularly coating, ink, fountain solution and agricultural compositions, manifesting reduced equilibrium and dynamic surface tension by the incorporation of a surface tension reducing amount of an acetylenic diol ethylene oxide/propylene oxide adduct of the structure: 
                 
 
where r and t are 1 or 2, (n+m) is 1 to 30 and (p+q) is 1 to 30.
 
     Also disclosed is a method for making random and block EO/PO adducts of acetylenic diols by reacting an acetylenic diol with EO and/or PO in the presence of a trialkylamine or Lewis acid.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation-in-part of application Ser.No. 09/304,607 filed May 4, 1999 now U.S. Pat. No. 6,313,182.

FIELD OF THE INVENTION

The invention relates to acetylenic diol alkylene oxide adducts, theirmanufacture and their use to reduce the surface tension in water-basedsystems.

BACKGROUND OF THE INVENTION

The ability to reduce the surface tension of water is of greatimportance in waterborne coatings, inks, adhesives, and agriculturalformulations because decreased surface tension translates to enhancedsubstrate wetting in actual formulations. Surface tension reduction inwater-based systems is generally achieved through the addition ofsurfactants. Performance attributes resulting from the addition ofsurfactants include enhanced surface coverage, fewer defects, and moreuniform distribution. Equilibrium surface tension performance isimportant when the system is at rest. However, the ability to reducesurface tension under dynamic conditions is of great importance inapplications where high surface creation rates are utilized. Suchapplications include spraying, rolling and brushing of coatings orspraying of agricultural formulations, or high speed gravure or ink-jetprinting. Dynamic surface tension is a fundamental quantity whichprovides a measure of the ability of a surfactant to reduce surfacetension and provide wetting under such high speed applicationconditions.

Traditional nonionic surfactants such as alkylphenol or alcoholethoxylates, and ethylene oxide (EO)/propylene oxide (PO) copolymershave excellent equilibrium surface tension performance but are generallycharacterized as having poor dynamic surface tension reduction. Incontrast, certain anionic surfactants such as sodium dialkylsulfosuccinates can provide good dynamic results, but these are veryfoamy and impart water sensitivity to the finished coating.

Surfactants based on acetylenic glycols such as2,4,7,9-tetramethyl-5-decyne-4,7-diol (1) and its ethoxylates (2) areknown for their good balance of equilibrium and dynamicsurface-tension-reducing capabilities with few of the negative featuresof traditional nonionic and anionic surfactants:

For many applications it would be desirable to produce acetylenic diolderivatives which have alternative properties. For example, inapplications in which excellent dynamic performance is required, it isoften desirable to have a surfactant which has higher criticalaggregation concentration (solubility limit or critical micelleconcentration) because higher bulk surfactant concentrations lead to ahigher diffusive flux of surfactant to newly created surface, andconsequently lower dynamic surface tension. Traditionally, acetylenicdiol surfactants with higher water solubility have been obtained byreaction of the parent with ethylene oxide; greater degrees ofethoxylation provide greater water solubility. Unfortunately, increasingthe level of ethoxylation also introduces a tendency to foam,introducing inefficiencies during formulation, defects duringapplication, and process issues in other applications.

Low dynamic surface tension is of great importance in the application ofwaterborne coatings. In an article, Schwartz, J. “The Importance of LowDynamic Surface Tension in Waterborne Coatings”, Journal of CoatingsTechnology, September 1992, there is a discussion of surface tensionproperties in waterborne coatings and a discussion of dynamic surfacetension in such coatings. Equilibrium and dynamic surface tension wereevaluated for several surface active agents. It is pointed out that lowdynamic surface tension is an important factor in achieving superiorfilm formation in waterborne coatings. Dynamic coating applicationmethods require surfactants with low dynamic surface tensions in orderto prevent defects such as retraction, craters, and foam.

Efficient application of agricultural products is also highly dependenton the dynamic surface tension properties of the formulation. In anarticle, Wirth, W.; Storp, S.; Jacobsen, W. “Mechanisms Controlling LeafRetention of Agricultural Spray Solutions”; Pestic. Sci. 1991, 33,411-420, the relationship between the dynamic surface tension ofagricultural formulations and the ability of these formulations to beretained on a leaf was studied. These workers observed a goodcorrelation between retention values and dynamic surface tension, withmore effective retention of formulations exhibiting low dynamic surfacetension.

Low dynamic surface tension is also important in high-speed printing asdiscussed in the article “Using Surfactants to Formulate VOC CompliantWaterbased Inks”, Medina, S. W.; Sutovich, M. N. Am. Ink Maker 1994, 72(2), 32-38. In this article, it is stated that equilibrium surfacetensions (ESTs) are pertinent only to ink systems at rest. EST values,however, are not good indicators of performance in the dynamic, highspeed printing environment under which the ink is used. Dynamic surfacetension is a more appropriate property. This dynamic measurement is anindicator of the ability of the surfactant to migrate to a newly createdink/substrate interface to provide wetting during high speed printing.

U.S. Pat. No. 5,098,478 discloses water-based ink compositionscomprising water, a pigment, a non ionic surfactant and a solubilizingagent for the nonionic surfactant. Dynamic surface tension in inkcompositions for publication gravure printing must be reduced to a levelof about 25 to 40 dynes/cm to assure that printability problems will notbe encountered.

U.S. Pat. No. 5,562,762 discloses an aqueous jet ink of water, dissolveddyes and a tertiary amine having two polyethoxylate substituents andthat low dynamic surface tension is important in ink jet printing.

In applications which require good dynamic performance and low foaming,acetylenic glycol-based surfactants have become industry standards. Thefollowing patents and articles describe various acetylenic alcohols andtheir ethoxylates as surface active agents:

U.S. Pat. No. 3,268,593 and Leeds, et al, I&EC Product Research andDevelopment 1965, 4, 237, disclose ethylene oxide adducts of tertiaryacetylenic alcohols represented by the structural formula:

wherein R₁ and R₄ are alkyl radicals having from 3-10 carbon atoms andR₂ and R₃ are methyl or ethyl and x and y have a sum in the range of 3to 60, inclusive. Specific ethylene oxide adducts include the ethyleneoxide adducts of 3-methyl-1-nonyn-3-ol,7,10-dimethyl-8-hexadecyne-7,10-diol;2,4,7,9-tetramethyl-5-decyne-4,7-diol and4,7-dimethyl-5-decyne-4,7-diol. Preferably, the ethylene oxide adductsrange from 3 to 20 units. Also disclosed is a process for themanufacture of materials of this type using trialkylamine catalysts.

U.S. Pat. No. 4,117,249 discloses 3 to 30 mole ethylene oxide (EO)adducts of acetylenic glycols represented by the structural formula:

wherein R is hydrogen or an alkenyl radical. The acetylenic glycols areacknowledged as having utility as surface active agents, dispersants,antifoaming nonionic agents, and viscosity stabilizers.

U.S. Pat. No. 5,650,543 discloses ethoxylated acetylenic glycols of theform:

where x and y are integers and the sum is from 2-50. These surfactantsare notable because they impart an ability to formulate coating and inkcompositions capable of high speed application.

JP 2636954 B2 discloses propylene oxide adducts of formula:

where R=C1-8 alkyl; m+n=integer 1 to 100. These compounds are preparedby reacting acetylenic glycols and propylene oxide in the presence ofLewis acid catalysts such as BF₃. It is stated that amine catalysts areinactive for the addition of propylene oxide to acetylenic diols. Thepropylene oxide adducts are said to be useful as wettability improversfor antirust oil, antifoamers, spreaders for pesticides, and wettingagents for adhesives. They are effective in improving wettability ofoils and have improved antifoaming ability.

JP 2621662 B2 describes dye or developing agent dispersions for thermalrecording paper containing propylene oxide (PO) derivatives of anacetylenic diol of the form:

where R1 and R2 are —CH3, —C2H5, —C4H9; R3 and R4 are —(OC3H4)mOH, or—OH where m is an integer 1-10.

JP 04071894 A describes coating solutions containing a dispersion of acolorless electron donating dye precursor and a dispersion of developer.At least one of them contains at least one type of wax having a meltingpoint of at least 60° C. and at least one EO or PO derivative of anacetylenic diol of the formula:

where R1 and R4 each represent methyl, ethyl, propyl, or butyl and R2and R3 are each —(OC2H5)nOH, or —(OC3H6)nOH (n is 1-10), or OH, mixedand dispersed.

JP 2569377 B2 discloses a recording material containing dispersions of asubstantially colorless electron donating dye precursor and a developer.When at least one of these dispersions is prepared, at least one of thecompounds:

where R³ and R⁶=methyl, ethyl, propyl or butyl; and R⁴ andR⁵=—(OC₂H₄)_(m)OH, —(OC₃H₆)_(m)OH (where m=an integer of 1-10) or —OH isadded.

JP 09150577 A discloses a heat sensitive recording medium which containsin the heat sensitive layer a leuco dye and 0.1-1.0 wt % of anethoxylate or propoxylate of an acetylenic glycol of the form:

where R¹=methyl, ethyl, propyl or butyl; R²=hydrogen or methyl; and nand m=1-10.

JP 04091168 A discloses silica which has been surface treated withcompounds of the form:

where R1=1-8C alkyl, A=2-3C alkylene glycol residue, R1 and A in amolecule may be the same or different, x and y=each an integer of 0-25.

JP 06279081 A describes a manufacturing process for a cementmortar-concrete hardening material to which 0.5-10 wt. % an acetylenicalcohol or diol alkoxylate is added together with fluorine groupsurfactants and/or silicon group surfactants. The acetylenic materialcan be expressed by the formula

where R1=H or —C(R2)(R3)(O(AO)nH); R2 and R3=1-8C alkyl radicals, A=2-3Calkylene radicals and n=0-30.

JP 03063187 A discloses the use of acetylenic glycol ethylene oxideand/or propylene oxide addition products in concentrated aqueousfountain solution compositions for offset printing. In one example, the8 to 12 mole ethylene oxide/1 to 2 mole propylene oxide adduct of3,5-dimethyl-4-octyne-3,5-diol is used in a fountain solution. Otherexamples illustrate the use of only ethylene oxide derivatives ofacetylenic diols.

JP 10-114880 discloses inkjet recording ink compositions containingalkoxylated acetylenic diols. Ethylene oxide, propylene oxide or bothrandom or block coaddition products are desirable as the alkylene oxideadded. The examples do not show any propoxylated materials.

Although acetylenic diol derivatives containing both ethylene oxide (EO)and propylene oxide (PO) have been taught as a general class ofmaterials, usually as potential extensions of work which had beenperformed with ethylene oxide derivatives, no actual examples of anacetylenic diol EO/PO derivative based upon2,4,7,9-tetramethyl-5-decyne-4,7-diol or2,5,8,11-tetramethyl-6-dodecyne-5,8-diol have been prepared andevaluated. There are no disclosures of any process which could be usedto prepare materials of this type.

SUMMARY OF THE INVENTION

This invention provides alkoxylated acetylenic diols which act assurfactants for water based compositions of the following structure:

where r and t are, preferably the same, 1 or 2, (n+m) is 1 to 30 and(p+q) is 1 to 30. The EO and PO units may be distributed along thealkylene oxide chain in blocks of EOs and POs or randomly.

This invention also relates to processes for the manufacture of certainalkoxylated acetylenic diols.

Another embodiment of the invention affords water-based compositionscontaining an organic or inorganic compound, particularly aqueousorganic coating, ink, and agricultural compositions, having reducedequilibrium and dynamic surface tension by incorporation of an effectiveamount of an alkoxylated acetylenic diol of the above structure.

It is desirable that an aqueous solution of the alkoxylated acetylenicdiol demonstrates a dynamic surface tension of less than 35 dynes/cm ata concentration of ≦0.5 wt % in water at 23° C. and 1 bubble/secondaccording to the maximum-bubble pressure method. Themaximum-bubble-pressure method of measuring surface tension is describedin Langmuir 1986, 2, 428-432, which is incorporated by reference.

Also provided is a method for lowering the equilibrium and dynamicsurface tension of aqueous compositions by the incorporation of thesealkoxylated acetylenic diol compounds.

Also provided is a method for applying a water-based inorganic ororganic compound-containing composition to a surface to partially orfully coat the surface with the water-based composition, the compositioncontaining an effective amount of an alkoxylated acetylenic diolcompound of the above structure for reducing the dynamic surface tensionof the water-based composition.

There are significant advantages associated with the use of thesealkoxylated acetylenic diols in water-based organic coatings, inks,fountain solutions for gravure printing processes, and agriculturalcompositions and these advantages include:

-   -   an ability to formulate water-borne compositions which may be        applied to a variety of substrates with excellent wetting of        substrate surfaces including contaminated and low energy        surfaces;    -   an ability to provide a reduction in coating or printing defects        such as orange peel and flow/leveling deficiencies;    -   an ability to produce water-borne coatings, fountain solutions        and inks which have low volatile organic content, thus making        these alkoxylated acetylenic diol surfactants environmentally        favorable;    -   an ability to formulate coating, fountain solution and ink        compositions capable of high speed application;    -   an ability to control the foaming characteristics of the        water-based compositions; and    -   an ability to produce some members of the class using a chemical        process similar to that used to produce acetylenic diol        ethoxylates.

Because of their excellent surfactant properties and the ability tocontrol foam, these materials are likely to find use in manyapplications in which reduction in dynamic and equilibrium surfacetension and low foam are important. Such uses include variouswet-processing textile operations, such as dyeing of fibers, fibersouring, and kier boiling, where low-foaming properties would beparticularly advantageous; they may also have applicability in soaps,water-based perfumes, shampoos, and various detergents where theirmarked ability to lower surface tension while simultaneously producingsubstantially no foam would be highly desirable.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to compounds of the formulas A and B. In formulaA:

(n+m) and (p+q) each can range from 1 to 30. It is preferred that (n+m)be 1.3 to 15 and most preferably 1.3 to 10. It is preferred that (p+q)be 1 to 10, more preferred 1-3 and most preferred 2. In Formula A, r andt are 1 or 2, especially r=t, i.e. the acetylenic diol portion of themolecule is 2,4,7,9-tetramethyl-5-decyne-4,7-diol or2,5,8,11-tetramethyl-6-dodecyne-5,8-diol.

The alkylene oxide moieties represented by (OC2H4) are the (n+m)polymerized ethylene oxide (EO) units and those represented by (OC3H6)are the (p+q) polymerized propylene oxide (PO) units. Products in whichthe EO and PO units are each segregated together are referred to as“block” alkoxylate derivatives. It is preferred the block copolymerproducts be capped, i.e., endcapped, with PO units.

The products in which the EO and PO units are randomly distributed alongthe polymer chain are referred to as “random” alkoxylate derivatives.Random derivatives can also be represented by formula B:

where R is hydrogen or methyl and (n+m)=2-60 with the proviso that thecompound contain at least one ethylene oxide unit, preferably at least1.3 EO units, and at least one propylene oxide unit, preferably at least2 PO units, and r and t are 1 or 2, especially r=t.

The block compositions of structure A can be prepared by reaction of2,4,7,9-tetramethyl-5-decyne-4,7-diol or2,5,8,11-tetramethyl-6-dodecyne-5,8-diol with the requisite quantitiesof ethylene oxide followed by propylene oxide in the presence of asuitable catalyst. Suitable catalysts include trialkylamines and Lewisacids, particularly BF₃. Alternatively, the compositions may be preparedby reaction of a pre-formed acetylenic diol ethoxylate with propyleneoxide in the presence of an appropriate catalyst. In the case of apre-formed acetylenic diol ethoxylate, it may be possible to use KOH orother alkali catalysts to effect the reaction with propylene oxide,provided the amount of ethylene oxide which has been added is sufficientto cover essentially all of the tertiary alcohol functionality.

The preferred process for making the acetylenic diol alkoxylates usesBF₃ or trialkylamine catalysts. The use of BF₃ allows the rapidpreparation of derivatives containing relatively large quantities ofpropylene oxide. However, compositions prepared with trialkylaminecatalysts, especially trimethylamine, are preferred for several reasons.They can be prepared using a process very similar to that used formanufacture of acetylenic diol ethoxylates without significant byproductchemistry. In particular, trialkylamine catalysts allow for thepreparation of 2 mole propylene oxide capped derivatives in highselectivity using a highly efficient, one pot process.

With respect to the processes for the preparation of acetylenic diolEO/PO adducts, the tertiary acetylenic diol starting materials can beprepared in various known manners such as those described in U.S. Pat.No. 2,250,445; U.S. Pat. No. 2,106,180 and U.S. Pat. No. 2,163,720,which are incorporated by reference. The acetylenic diol startingmaterial may contain from 8 to 26 carbons. It is preferred that theacetylenic diol starting material contain 14 to 16 carbons, and it ismost particularly preferred that it be2,4,7,9-tetramethyl-5-decyne-4,7-diol or2,5,8,11-tetramethyl-6-dodecyne-5,8-diol.

Various basic catalysts can be used to promote the reaction between thealkylene oxide and the acetylenic tertiary glycols in which the hydroxylgroups are attached to a carbon atom in a position alpha to theacetylenic bonds according to this invention. Tertiary aliphatic amines,namely trialkylamines such as trimethylamine, triethylamine,tripropylamine, dimethylethylamine, diethylmethylamine and the like, areparticularly advantageous catalysts for the reaction. Such tertiaryaliphatic amines catalyze the addition reaction at a rapid rate atmoderately low temperatures and pressures without inducing cleavage ofthe acetylenic glycol. Trimethylamine is preferred because of its highcatalytic activity and longevity in the reaction.

As is known in the art, the use of strongly basic catalysts such assodium hydroxide, especially at high temperatures of about 150° C.,induces cleavage of the acetylenic tertiary glycols and for this reasonshould be avoided, unless of course, sufficient ethylene oxide has beenadded to prevent substantial decomposition of tertiary acetylenicalcohol functionality. Once the tertiary hydroxyl groups of theacetylenic glycol have reacted with ethylene oxide, the resultant adductexhibits the marked stability of an ether. So stable are the adductsthat they can be heated with concentrated base such as sodium hydroxideat elevated temperatures, while comparable treatment of the initialacetylenic glycol is accompanied by extensive degradation. Consequently,strongly basic catalysts, such as the alkali metal hydroxides, can beused to increase the polyalkylene oxide chain length once the initialadducts have been formed and protected against decomposition. It isanticipated that alkali metal hydroxides could also be used to promotethe addition of propylene oxide to initial EO or PO adducts withsufficiently low quantities of residual tertiary acetylenic alcoholfunctionality.

The trialkylamine-catalyzed addition reaction may be performed at eitheratmospheric (15 psig; 1 bar) or moderate to low superatmosphericpressures (30-300 psig; 2-20 bar). The use of moderate to lowsuperatmospheric pressures is preferred since it obviates the necessityof recycling unreacted ethylene oxide and propylene oxide, and generallyproceeds at faster rates than additions carried out at atmosphericpressures. The effect of pressure on rate is particularly important inthe reaction with propylene oxide, and it is therefore preferred thatreactions be performed at pressures in excess of 30 psig (2 bar). It isparticularly preferred that the process be carried out at a pressuregreater than 60 psig (4 bar). Another benefit of performing the reactionunder pressure is that such reactions may be accomplished with ordinaryefficient agitation, while reactions conducted at atmospheric pressureoften work best when a dispersion type agitator is used. While thereaction can be carried out at lower pressure, reaction rates, andtherefore reactor productivity, suffer. Performing the reaction atpressures much in excess of about 300 psig (20 bar) would likely haveonly marginal benefit, and would increase the cost of equipment requiredfor manufacture. It is preferred to operate at 100 psig (6.7 bar).

The temperature at which the reaction is run for trialkylamine catalyzedreactions will depend upon the particular system and the catalystconcentration. Generally, at higher catalyst concentrations, thereactions can be run at lower temperatures and pressures. Reactiontemperatures should be high enough to permit the reaction to proceed ata reasonable rate, but low enough to prevent decomposition of thereagents and products. Temperatures in the range of 40-150° C. aresuitable, 50-120° C. preferred, and 70-90° C. particularly preferred.

In the trialkylamine catalyzed process in which propylene oxide is addedto an acetylenic diol EO adduct, the reaction stops at a PO end cap oneach chain, i.e., the obtained product is an acetylenic diol EO/POadduct containing two PO end caps, p and q each being 1 in Formula A.When a mixture of EO and PO is added to an acetylenic diol or diol EOadduct, the trialkylamine catalyzed process affords an adduct havingrandom EO and PO units, in the latter case extending beyond the originalEO block.

To prepare the EO/PO adducts of the invention, the acetylenic glycol isliquefied by melting and the catalyst is added with stirring. Ethyleneoxide and/or propylene oxide are added as liquids with stirring and thereaction is concluded when the desired polyalkylene oxide chain lengthis reached as determined by gel permeation chromatography (GPC), highperformance liquid chromatography (HPLC), nuclear magnetic resonance(NMR), cloud point (ASTM D2024-65) or water titration of an isopropylalcohol solution. No solvents are necessary during the reaction, butinert solvents such as aromatic hydrocarbons (benzene and toluene) andethers (ethyl ether) may be used to facilitate handling. In someinstances it may be convenient to use a low mole ethoxylated acetylenicdiol, since these products are liquids and are therefore easy to handle.

In reactions catalyzed by Lewis acids, the reaction conditions will bedetermined by the identity and concentration of the catalyst. Examplesof Lewis acid catalysts include BCl₃, AlCl₃, TiCl₄, BF₃, SnCl₄, ZnCl₂and the like. The preferred Lewis acid catalyst is BF₃. In BF₃ catalyzedreactions, temperature control during the initial stages of the reactionis critical, since too high a temperature will result in dehydration ofthe acetylenic diol. It is preferred that the temperature be maintainedbelow 80° C., preferably below 60° C., and most preferably below 50° C.The reaction pressure can range from atmospheric to low to moderatesuperatmospheric pressure, i.e., from 15 to 300 psig (1 to 20 bar).Because of the high activity of BF₃, good results can be obtained atmore moderate pressures of about 1 bar than for those reactionsperformed using trialkylamine catalysts.

In adding liquid alkylene oxide(s) to the acetylenic glycol and thecatalyst, care should be taken to avoid the presence of an excess ofalkylene oxide(s) in the reaction mixture since the reaction is veryexothermic and could prove to be very hazardous. The danger of anuncontrollable reaction can be avoided by adding the alkylene oxide(s)in a manner and at a rate such that the alkylene oxide(s) are reactedessentially as rapidly as they are introduced into the reaction mixture.The formation of a flammable mixture in the headspace is best avoided bypressuring the reactor headspace to a sufficient pressure with an inertgas such as nitrogen such that the alkylene oxide(s) remains below itslower explosive limit (LEL).

In the both the Lewis acid catalyzed and the trialkylamine catalyzedprocesses, the catalysts may be used at 0.001 to 10 wt %, preferably0.01 to 5 wt %, and most preferably 0.1 to 1 wt %, based on total finalreactant mass. In both cases, because deactivation may occur during thealkoxylation, it may be necessary to add additional catalyst to completethe reaction, particularly if large amounts of EO and PO are beingadded.

In the processes for making the randomly distributed EO/PO adducts, theEO and PO may be added to the reaction concurrently as separate chargesor streams, or added as a single charge or stream comprising a mixtureof EO and PO. In making block EO/PO adducts the EO and PO are addedconsecutively.

The alkoxylated acetylenic diols are useful for the reduction ofequilibrium and dynamic surface tension in water-based compositionscontaining an organic compound, particularly aqueous coating, ink,fountain solution and agricultural compositions containing organiccompounds such as polymeric resins, macromolecules, herbicides,insecticides or plant growth modifying agents. It is desirable that anaqueous solution of the alkoxylated acetylenic diol demonstrates adynamic surface tension of less than 35 dynes/cm at a concentration of≦0.5 wt % in water at 23° C. and 1 bubble/second according to themaximum-bubble-pressure method. The maximum-bubble-pressure method ofmeasuring surface tension is described in Langmuir 1986, 2, 428-432,which is incorporated by reference.

In one aspect of the invention certain alkoxylated acetylenic diols ofthe above formula display excellent ability to reduce equilibrium anddynamic surface tension while producing substantially no foam.

The alkoxylated acetylenic diols are suitable for use in an aqueouscomposition comprising in water an inorganic compound which is a mineralore or a pigment or an organic compound which is a pigment, apolymerizable monomer, such as addition, condensation and vinylmonomers, an oligomeric resin, a polymeric resin, a macromolecule suchas gum arabic or carboxymethyl cellulose, a detergent, a causticcleaning agent, a herbicide, especially a herbicide forchlorophyll-containing plants, an insecticide, or a plant growthmodifying agent.

An amount of the alkoxylated acetylenic diol compound that is effectiveto reduce the equilibrium and/or dynamic surface tension of thewater-based, organic or inorganic compound-containing composition isadded. Such effective amount may range from 0.001 to 10 g/100 mL,preferably 0.01 to 1 g/100 mL, and most preferably 0.05 to 0.5 g/100 mLof the aqueous composition. Naturally, the most effective amount willdepend on the particular application and the solubility of theparticular alkoxylated acetylenic diol.

In the following water-based organic coating, ink, fountain solution andagricultural compositions containing an alkoxylated acetylenic diolaccording to the invention, the other listed components of suchcompositions are those materials well known to the workers in therelevant art.

A typical water-based protective or decorative organic coatingcomposition to which the alkoxylated acetylenic diol surfactants of theinvention may be added would comprise the following components in anaqueous medium at 30 to 80 wt % ingredients:

Typical Water-Based Organic Coating Composition 0 to 50 wt % PigmentDispersant/Grind Resin 0 to 80 wt % Coloring Pigments/ExtenderPigments/Anti-Corrosive Pigments/Other Pigment Types 5 to 99.9 wt %Water-Borne/Water-Dispersible/Water-Soluble Resins 0 to 30 wt % SlipAdditives/Antimicrobials/Processing Aids/ Defoamers 0 to 50 wt %Coalescing or Other Solvents 0.01 to 10 wt % Surfactant/WettingAgent/Flow and Leveling Agents 0.01 to 5 wt % Acetylenic Diol EO/PODerivative

A typical water-based ink composition to which the alkoxylatedacetylenic diol surfactants of the invention may be added would comprisethe following components in an aqueous medium at 20 to 60 wt %ingredients:

Typical Water-Based Ink Composition 1 to 50 wt % Pigment 0 to 50 wt %Pigment Dispersant/Grind Resin 0 to 50 wt % Clay base in appropriateresin solution vehicle 5 to 99.9 wt %Water-Borne/Water-Dispersible/Water-Soluble Resins 0 to 30 wt %Coalescing Solvents 0.01 to 10 wt % Surfactant/Wetting Agent 0.01 to 10wt % Processing Aids/Defoamers/Solubilizing Agents 0.01 to 5 wt %Acetylenic Diol EO/PO Derivative

A typical water-based agricultural composition to which the alkoxylatedacetylenic diol surfactants of the invention may be added would comprisethe following components in an aqueous medium at 0.1 to 80 wt %ingredients:

Typical Water-Based Agricultural Composition 0.1 to 50 wt % Insecticide,Herbicide or Plant Growth Modifying Agent 0.01 to 10 wt % Surfactant 0to 5 wt % Dyes 0 to 20 wt % Thickeners/Stabilizers/Co-surfactants/GelInhibitors/Defoamers 0 to 25 wt % Antifreeze 0.01 to 50 wt % AcetylenicDiol EO/PO Derivative

A typical fountain solution composition for planographic printing towhich the alkoxylated acetylenic diol surfactants of the invention maybe added would comprise the following components in an aqueous medium at30 to 70 wt % ingredients:

Typical Fountain Solution for Planographic Printing 0.05 to 30 wt % Filmformable, water soluble macromolecule 1 to 75 wt % Alcohol, glycol, orpolyol with 2-12 carbon atoms, water soluble or can be made to be watersoluble 0.01 to 60 wt % Water soluble organic acid, inorganic acid, or asalt of thereof 0.01 to 50 wt % Acetylenic Diol EO/PO Derivative

EXAMPLE 1

This example illustrates that two mole propoxylates of acetylenic diolethoxylates can be prepared with high selectivity when usingtrialkylamine catalysts. In this example, the preparation of the 7 molepropoxylate of Surfynol® 465 surfactant, which is the 10 mole ethoxylateof 2,4,7,9-tetramethyl-4-decyne-4,7-diol, was attempted.

A 1000 mL autoclave was charged with Surfynol® 465 surfactant (300 g,0.45 moles) and dimethylethylamine (53.7 g, 0.73 moles). The reactor wassealed, purged free of air with three nitrogen pressure-vent cycles,then pressured to 100 psig (6.7 bar) with nitrogen and heated to 120° C.Propylene oxide (183 g, 3.15 moles) was added over a period of 70minutes by means of a syringe pump. At the completion of the addition,the reaction mixture was heated for an additional 12 hr at 120° C. Thereactor contents were cooled and discharged. The product was heatedunder vacuum to remove volatiles (unreacted PO and catalyst); 68 g ofmaterial were removed.

Matrix assisted laser desorption/ionization mass spectrometry (MALD/I)indicated that almost all the individual oligomers in the productpossessed one or two propylene oxide residues with only very smallamounts of product containing three or more PO units. The fate of asubstantial amount of the propylene oxide appeared to be formation ofdimethylamino-terminated polypropyleneoxide.

These results are consistent with relatively facile reaction of primaryhydroxyl with propylene oxide, but only very sluggish reaction ofpropylene oxide terminated chains. It appears that after EO-terminatedchains react with one propylene oxide, chain growth essentially stops.Since there are approximately two EO chains for each starting acetylenicdiol, high selectivity to the two mole propoxylate results. In thisenvironment, decomposition of the catalyst to formdimethylamino-terminated polypropylene oxide is the predominantreaction.

It would not be anticipated based on the teachings of JP 2636954 B2 thattrialkylamine catalysts would have any efficacy for promoting thereaction of propylene oxide. It would also not be anticipated that highselectivity to the two mole propoxylates of an acetylenic diol could beachieved.

EXAMPLES 2-5

Example 3 illustrates the preparation of the 3.5 mole ethoxylate of2,4,7,9-tetramethyl-5-decyne-4,7-diol capped with 2 moles of propyleneoxide using trimethylamine catalyst and a preformed ethoxylate. The 3.5mole ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol is commerciallyavailable from Air Products and Chemicals, Inc. and is marketed asSurfynol® 440 surfactant.

A 1000 mL autoclave was charged with Surfynol® 440 surfactant (400 g,1.05 moles) which had previously been dried by heating under nitrogen.The reactor was sealed and pressure checked, the air was removed withthree nitrogen pressure-vent cycles, and trimethylamine (2.7 g, 0.5 wt %of final reaction mass) was added by means of a gas tight syringe. Thereactor was pressured to 100 psig (6.7 bar) with nitrogen and heated to100° C. whereupon propylene oxide (122 g, 147 mL, 2.10 moles) was addedat a rate of 1.0 mL/min by means of a syringe pump. At the completion ofthe addition, the reactor contents were stirred at 100° C. for 14.5hours. The reactor was cooled and the contents were discharged into around bottomed flask and heated under vacuum (0.25 torr) at ambienttemperature (ca. 23° C.) for 16 hours to remove the trimethylaminecatalyst. The product was characterized by nuclear magnetic resonance(NMR) spectrometry. The data are summarized in Table 1 which showsacetylenic diol compositions prepared using trimethylamine catalysis.

Other ethylene oxide/propylene oxide derivatives of2,4,7,9-tetramethyl-5-decyne-4,7-diol (Examples 2, 4 and 5) wereprepared in a similar manner. The compositions are also summarized inTable 1.

Since JP 2636954 B2 states that amines are inactive for the addition ofpropylene oxide, it would not be anticipated that trimethylamine wouldbe an effective catalyst for the preparation of an EO/PO derivative of2,4,7,9-tetramethyl-5-decyne-4,7-diol.

TABLE 1 Theoretical Determined by NMR Example EO Moles PO Moles EO MolesPO Moles 2 1.3 2.0 1.5 1.9 3 3.5 2.0 3.9 1.8 4 5.1 2.0 5.9 2.0 5 10.02.0 10.7 2.0

EXAMPLES 6-21

These examples illustrate the preparation of ethylene oxide/propyleneoxide derivatives of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (designatedS104) and 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol (designated S124)using BF₃ catalyst. To our knowledge a procedure for the preparation ofethylene oxide/propylene oxide derivatives of acetylenic diols usingLewis acids such as BF₃ has not previously been disclosed. The procedureis illustrated for the preparation of the 5 mole ethylene oxide, 2 molepropylene oxide adduct of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (S104)in which the EO and PO units are randomly situated along the alkyleneoxide chain.

A 1000 mL autoclave was charged with the 1.3 mole ethylene oxide adductof 2,4,7,9-tetramethyl-5-decyne-4,7-diol (313 g, 1.1 moles; Surfynol 104surfactant from Air Products and Chemicals, Inc.) which had previouslybeen dried by heating under vacuum. The reactor was sealed and pressurechecked, the air was removed with three nitrogen pressure-vent cycles.The reactor was pressured to 100 psig (6.7 bar) with nitrogen, and thecontents were heated to 40° C. BF₃ diethyl etherate (1.3 g) was addedand ethylene oxide and propylene oxide were added simultaneously atrates of 91.05 mL/h and 68.95 mL/h, respectively, by means of twosyringe pumps. The total amount of ethylene oxide (180 g, 204 mL, 4.08moles) and propylene oxide (128 g, 155 mL, 2.2 moles) were such that thefinal mole ratio of diol:EO:PO was 1:5:2. After the completion of theaddition, an additional 0.7 g of BF₃ diethyl etherate was added,whereupon an exotherm to 45.5° C. was observed. At this point gaschromatographic analysis indicated that the reaction was complete. Theproduct (Example 6) was analyzed by NMR and MALD/I and found to have astructure consistent with the desired structure.

Sixteen similar materials (Examples 7-22) were prepared by variation ofthe diol structure, the amounts of ethylene oxide and propylene oxide,and the structural motif of the alkylene oxide chain. Table 2 shows theacetylenic diol compositions prepared using BF₃ catalysis. In Table 2, Rdesignates “random,” while B designates “block.”

The composition of Example 22 has been disclosed in JP 03063187 A(however, JP '187 does not teach a method for its preparation norwhether the adduct is a block or random copolymer), and has been shownto have efficacy in fountain solutions for lithographic printing. TheS82 designation corresponds to 3,6-dimethyl-4-hexyne-3,6-diol.

TABLE 2 Theoretical Determined by NMR Example Diol R/B EO Moles PO MolesEO Moles PO Moles 6 S104 R 5 2 6.5 2.9 7 S104 B 5 2 5.5 2.2 8 S104 R 510 3.2 11.5 9 S104 B 5 10 3.5 11.1 10 S104 R 15 2 16.2 2.2 11 S104 B 152 14.4 2.1 12 S104 R 15 10 17.3 8.6 13 S104 B 15 10 15.0 9.7 14 S124 R 52 6.9 3.2 15 S124 B 5 2 4.8 2.2 16 S124 R 5 10 8.0 7.6 17 S124 B 5 105.1 10.0 18 S124 R 15 2 16.3 1.9 19 S124 B 15 2 14.9 2.1 20 S124 R 15 1015.4 9.3 21 S124 B 15 10 13.6 8.1 22 S82  B 10 2 9.6 1.9

In the following Examples dynamic surface tension data were obtained foraqueous solutions of various compounds using the maximum bubble pressuremethod at bubble rates from 0.1 bubbles/second (b/s) to 20 b/s. Themaximum bubble pressure method of measuring surface tension is describedin Langmuir 1986, 2, 428-432. These data provide information about theperformance of a surfactant at conditions from near-equilibrium (0.1b/s) through extremely high surface creation rates (20 b/s). Inpractical terms, high bubble rates correspond to high printing speeds inlithographic printing, high spray or roller velocities in coatingapplications, and rapid application rates for agricultural products.

COMPARATIVE EXAMPLE 25

Dynamic surface tension data were obtained for aqueous solutions of thecomposition of Example 22 (S82/10 EO/2PO/B) using the maximum bubblepressure technique. This material has been disclosed in JP 03063187 Aand is taught as a component in an aqueous fountain solutioncomposition. The surface tensions were determined at bubble rates from0.1 bubbles/second (b/s) to 20 b/s. The data are presented in Table 3.

TABLE 3 Dynamic Surface Tension (dyne/cm)-Example 22 Concentration (wt%) 0.1 b/s 1 b/s 6 b/s 15 b/s 20 b/s 0.1 39.1 42.3 46.5 51.6 53.0 1.034.4 34.9 35.5 37.7 38.5 5.0 33.8 34.0 34.7 36.3 36.4

The data illustrate that this product is reasonably effective atreducing the surface tension of water, although relatively highconcentrations are required to obtain reasonable performance.

EXAMPLE 26

Solutions in distilled water of 10 mole EO/2 mole PO block derivative of2,4,7,9-tetramethyl-5-decyne-4,7-diol (Example 5) were prepared andtheir dynamic surface tension properties were measured using theprocedure described above. The data are set forth in the Table 4.

TABLE 4 Dynamic Surface Tension (dyne/cm)-Example 5 Concentration (wt %)0.1 b/s 1 b/s 6 b/s 15 b/s 20 b/s 0.1 40.5 42.0 44.3 47.1 48.1 0.5 32.433.6 35.1 36.6 37.2 1.0 29.8 30.5 32.1 33.0 33.7

These data illustrate that the composition of this invention is markedlysuperior in its ability to reduce surface tension relative to thecomposition of the prior art. Comparison of the data for the 1.0 wt %solution of the Example 5 surfactant with that of the 5.0 wt % solutionof the S82 derivative (Example 22) shows that the compound of theinvention provides superior performance at all surface creation rates at20% the use level. Since reduction of dynamic surface tension is of suchimportance in a dynamic application in which aqueous fountain solutionsare utilized, it would not be anticipated based on the teachings of theprior art that modification of the hydrophobic group (the acetylenicdiol moiety) would have such an advantageous effect.

COMPARATIVE EXAMPLES 27-31

Solutions in distilled water of the 1.3, 3.5, 5.1, and 10 moleethoxylates of 2,4,7,9-tetramethyl-5-decyne-4,7-diol were prepared. The1.3, 3.5, and 10 mole ethoxylates are marketed by Air Products andChemicals, Inc. as Surfynol® 420, 440, and 465 surfactants,respectively. Their dynamic surface tensions were measured using theprocedure described above, and these data were used to determine thequantities provided in Table 5.

The pC₂₀ value is defined as the negative logarithm of the molarconcentration of surfactant required to decrease the surface tension ofan aqueous solution to 52.1 dyne/cm, that is, 20 dyne/cm below that ofpure water when the measurement is performed at 0.1 b/s. This value is ameasure of the efficiency of a surfactant. In general, an increase inpC₂₀ value of 1.0 indicates that 10 times less surfactant will berequire to observe a given effect.

The critical aggregation concentrations (solubility limit or criticalmicelle concentration) were determined by intersection of the linearportion of a surface tension/in concentration curve with the limitingsurface tension as is described in many textbooks. The limiting surfacetensions at 0.1 and 20 bubbles/second (b/s) represent the lowest surfacetensions in water which can be achieved at the given surface creationrate for a given surfactant regardless of the amount of surfactant used.These values give information about the relative ability to a surfactantto reduce surface defects under near-equilibrium condition (0.1 b/s)through very dynamic conditions (20 b/s). Lower surface tensions wouldallow the elimination of defects upon application of a formulation ontolower energy surfaces.

The foaming properties of 0.1 wt % solutions of the prior artsurfactants were examined using a procedure based upon ASTM D 1173-53.In this test, a 0.1 wt % solution of the surfactant is added from anelevated foam pipette to a foam receiver containing the same solution.The foam height is measured at the completion of the addition (“InitialFoam Height”) and the time required for the foam to dissipate isrecorded (“Time to 0 Foam”). This test provides a comparison between thefoaming characteristics of various surfactant solutions. In general, incoatings, inks, and agricultural formulations, foam is undesirablebecause is complicates handling and can lead to coating and printdefects, and to inefficient application of agricultural materials.

TABLE 5 Sol limiting γ γ (0.1% solution) RM Foam Structure pC₂₀ Limit0.1 b/s 20 b/s 1 b/s 6 b/s initial (t to 0) Example 27 3.74 0.1 32.140.3 33.1 36.4 2.0 (3 s)

Example 28 3.84 0.18 28.8 31.7 32.8 34.2 0.5 (3 s)

Example 29 3.90 0.29 26.9 29.3 34.3 36.2 1.4 (9 s)

Example 30 3.95 0.40 26.9 29.8 36.1 38.3 1.3 (32 s)

Example 31 3.79 (0.89) 29.0 32.7 42.5 44.8 1.5 (0.6 cm)

Example 32 3.43 (2.91) 35.7 39.9 51.5 53.2 1.5 (0.6 cm)

EXAMPLES 33-36

Surface tension and foam data were obtained in a similar manner for thesurfactants of Examples 1-4 based on2,4,7,9-tetramethyl-5-decyne-4,7-diol. The data are set forth in Table6.

TABLE 6 Sol limiting γ γ (0.1% solution) RM Foam Structure pC₂₀ Limit0.1 b/s 20 b/s 1 b/s 6 b/s initial (t to 0) Example 33 3.51 0.07 31.640.6 33.4 40.6 1.6 (3 s)  1.3 EO/2 PO (Example 2) Example 34 4.07 0.2129.3 31.4 33.6 36.6 1.0 (10 s) 3.5 EO/2 PO (Example 3) Example 35 4.130.32 27.3 29.9 35.3 37.6 0.3 (6 s)  5.1 EO/2 PO (Example 4) Example 364.05 (0.78) 29.8 33.7 42.0 44.3 2.1 (1.3) 10 EO/2 PO (Example 5)

The data in Table 6 illustrate that propoxylation with 2 moles ofpropylene oxide in the presence of trimethylamine resulted insurfactants with higher efficiencies than their unpropoxylatedcounterparts. This effect is reflected in both the pC₂₀ values, whichincrease by about 0.2 units, and the surface tension results for 0.1 wt% solutions at 1 b/s, which decrease by about a dyne/cm. In addition,the foaming characteristics of the surfactants change significantly as aresult of modification with propylene oxide. This change can be eitherin the direction of greater foam (e.g. for the 10 and 30 moleethoxylates) or to lesser foam (for the 5.1 mole ethoxylate). Theability to control foam is advantageous in many applications, includingcoatings, inks, adhesives, fountain solutions, agriculturalformulations, soaps and detergents.

EXAMPLES 37-52

Solutions in distilled water of the materials of Examples 37-52 wereprepared and their surface tension and foam performance were evaluatedas in the example above. The results are set forth in the Table 7.

TABLE 7 limiting γ^(a) γ (0.1% solution)^(a) RM Foam^(b) Structure pC₂₀CAG^(c) 0.1 b/s 20 b/s 1 b/s 6 b/s initial (t to 0) Example 37 4.16 0.1028.6 31.2 30.0 37.1 1.1 (5 s) 104/5/2/R (Example 6) Example 38 4.15 0.1127.9 33.1 33.6 38.4 1.9 (4 s) 104/5/2/B (Example 7) Example 39 4.50 0.0431.2 35.0 33.7 39.9 0.5 (1 s) 104/5/10/R (Example 8) Example 40 4.580.08 31.0 34.1 37.2 40.5 0.5 (10 s) 104/5/10/B (Example 9) Example 414.20 0.07 28.3 30.7 36.0 43.8 4.5 (1.1 cm) 104/15/2/R (Example 10)Example 42 5.04 0.18 27.6 31.7 36.8 42.9 5.3 (0.5 cm) 104/15/2/B(Example 11) Example 43 4.42 0.05 28.8 30.9 33.8 44.5 2.8 (0.7 cm)104/15/10/R (Example 12) Example 44 4.35 0.09 28.3 34.4 35.5 45.6 4.0(0.4 cm) 104/15/10/B (Example 13) Example 45 4.39 0.03 26.5 30.8 28.233.5 2.4 (0.2 cm) 124/5/2/R (Example 14) Example 46 4.42 0.04 26.9 29.728.5 32.5 3.0 (0.3 cm) 124/5/2/B (Example 15) Example 47 4.57 0.02 30.336.7 31.8 40.8 1.8 (0.3 cm) 124/5/10/R (Example 16) Example 48 4.56 0.0231.3 36.2 33.4 40.3 1.4 (12 s) 124/5/10/B (Example 17) Example 49 4.360.06 27.9 32.2 30.5 40.8 2.6 (1.3 cm) 124/15/2/R (Example 18) Example 504.16 0.02 27.9 35.6 31.1 42.5 2.5 (1.2 cm) 124/15/2/B (Example 19)Example 51 4.58 0.06 29.1 32.3 32.8 43.2 2.0 (1.0 cm) 124/15/10/R(Example 20) Example 52 4.55 0.05 28.0 33.3 33.7 41.4 4.8 (1.0 cm)124/15/10/B (Example 21) ^(a)dyne/cm. ^(b)Ross-Miles foam: cm (time to 0foam in seconds or cm after 5 minutes) ^(c)Critical aggregationconcentration (wt %).

These data illustrate variation of the acetylenic diol structure, the EOand PO content, and the structural motif of these surfactants allowstailoring of the surfactant properties to a specific application.Surfactants with very low foam (Examples 39 and 40) or relatively highfoam (Examples 41 and 42) can be produced. In addition, most of thesematerials exhibit excellent dynamic surface tension performance, asshown by their limiting surface tension values at 20 b/s. Thecombination of properties will be of value in many applications,including coatings, inks, adhesives, fountain solutions, agriculturalformulations, soaps and detergents.

EXAMPLE 53

2,4,7,9-Tetramethyl-5-decyne-4,7-diol was ethoxylated to produce the 5.1mole ethoxylate using trimethylamine catalyst and a procedure similar tothat of Examples 2-5. A small sample was withdrawn, and sufficientpropylene oxide was added to produce the 0.4 mole propoxylate. Again asample was withdrawn. Similarly, more propylene oxide was added toproduce the 0.9 and 1.4 mole propylene oxide adducts. In a separate run,the 2.0 mole propoxylate of the 5.1 mole ethoxylate was prepared.

Surface tension (γ) and foam data were obtained for the propoxylates of5.1 mole ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol asdescribed above. The data are set forth in the Table 8.

TABLE 8 γ (0.1 wt % solution)^(a) moles 0.1 1 6 15 20 RM Foam^(b) Ex POpC₂₀ b/s b/s b/s b/s b/s Initial (t to 0) 53A 0 3.95 35.1 36.2 38.1 42.044.4 1.6 (0.7 cm) 53B 0.4 3.74 34.8 35.8 37.9 42.0 44.4 1.4 (0.3 cm) 53C0.9 3.72 34.9 35.9 38.2 42.7 45.3 1.4 (27 s) 53D 1.4 3.79 34.6 35.9 38.342.0 44.5 1.2 (21 s) 53E 2.0 4.13 34.0 35.3 37.6 41.5 43.3 0.6 (6 s)^(a)dyne/cm ^(b)Initial foam heights in cm (foam height after 5 min, ortime to 0 foam).

The data in Table 8 show that while propoxylation up to 2 PO units haslittle impact on the surface tension performance of the 5.1 moleethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol, it has asignificant positive impact on foam control, with greater controlobserved with higher degrees of propoxylation. Such an effect has notpreviously been observed with alkoxylated derivatives of acetylenicdiols. The ability to control foam is of crucial importance in theapplication of many waterborne formulations, because foam generallyleads to defects.

EXAMPLE 54

In these examples additional ethoxylated acetylenic diols weresynthesized.

The two base acetylenic diols that were ethoxylated were of the abovestructure, namely, S-104 (2,4,7,9-tetramethyl-5-decyne-4,7-diol) inwhich r and t are both 1, i.e., an isobutyl group, and S-124(2,5,8,11-tetramethyl-6-dodecyne-5,8-diol) in which r and t are both 2,i.e., an isoamyl group.

Following the procedures set forth previously herein, dynamic surfacetension (γ) data, foaming data and surfactant efficiency (pC₂₀) datawere collected for the ethoxylated materials. The surfactant efficiencypC₂₀ value is defined as the negative logarithm of the molarconcentration of surfactant required to decrease the surface tension ofan aqueous solution to 52.1 dyne/cm, that is, 20 dyne/cm below that ofpure water when the measurement is performed at 0.1 b/s. This value(pC₂₀) is a measure of the efficiency of a surfactant. In general, anincrease in pC₂₀ value of 1.0 indicates that 10 times less surfactantwill be require to observe a given effect, i.e., the higher the valuethe more efficient the surfactant.

The S-104 ethoxylates were made using the 5.1 mole ethoxylate of2,4,7,9-tetramethyl-5-decyne4,7-diol which was prepared by reaction ofthe starting diol with ethylene oxide in the presence of trimethylaminecatalyst at 80° C. using conventional procedures. This 5.1 moleethoxylate of S-104 was reacted with varying amounts of ethylene oxideusing trimethylamine catalyst. A 1000 mL autoclave was charged with the5.1 mole ethoxylate (210 g, 0.47 moles) which had previously been driedby heating under nitrogen. The reactor was sealed and pressure checked,the air was removed with three nitrogen pressure-vent cycles, andtrimethylamine (1.2 g) was added by means of a gas tight syringe. Thereactor was pressured to 100 psig (6.7 bar) with nitrogen and heated to100° C. whereupon ethylene oxide (8.2 g, 9.3 mL, 0.19 moles) was addedat a rate of 1 mL/min by means of a syringe pump. At the completion ofthe addition, the reactor contents were stirred at 100° C. for 4 hours.The reactor was sampled to obtain an aliquot of the 5.5 mole ethoxylateof 2,4,7,9-tetramethyl-5-decyne-4,7-diol. Higher ethoxylates wereprepared by adding sufficient ethylene oxide to prepare the 6.5, 7.1,15, 17, and 25 mole ethoxylates of2,4,7,9-tetramethyl-5-decyne-4,7-diol. Samples of each ethoxylate wereremoved from the reactor and characterized by matrix assistedlaser-desorption/ionization (MALD/I) analysis.

The surface tension γ and foam data in Table 9 were obtained for 0.1 wt% aqueous solutions of these S-104 ethoxylates. Table 9 also shows theefficiency pC₂₀ data.

TABLE 9 Additional Total γ γ γ γ γ RM Foam Ex Moles EO EO pC₂₀ 0.1 b/s 1b/s 6 b/s 15 b/s 20 b/s Initial (t to 0) 54A 0.4 5.5 3.90 36.6 37.7 40.042.8 42.3 1.5 cm (34 s) 54B 1.4 6.5 3.78 38.2 39.4 41.9 45.2 45.2 1.5 cm(32 s) 54C 2.0 7.1 3.84 38.8 40.1 42.6 45.7 45.3 1.5 cm (32 s) 54D 9.915 3.57 45.9 47.6 49.9 52.4 53.7 1.5 cm (2 m 27 s) 54E 11.9 17 3.40 46.948.6 50.6 52.8 54.1 1.5 cm (30 s) 54F 19.9 25 3.34 49.8 51.6 53.3 55.256.3 1.3 cm (59 s)

The S-124 ethoxylates were made using the 4 mole ethoxylate of2,5,8,11-tetramethyl-6-dodecyne-5,8-diol, which is commerciallyavailable as Dynol 604 surfactant from Air Products and Chemicals, Inc.This 4 mole ethoxylate of S-124 was reacted with ethylene oxide usingtrimethylamine catalyst. A 1000 mL autoclave was charged with the 4.0mole ethoxylate (195 g, 0.44 moles) which had previously been dried byheating under nitrogen. The reactor was sealed and pressure checked, theair was removed with three nitrogen pressure-vent cycles, andtrimethylamine (1.2 g) was added by means of a gas tight syringe. Thereactor was pressured to 100 psig (6.7 bar) with nitrogen and heated to100° C. whereupon ethylene oxide (58.31 g, 66.1 mL, 1.32 moles) wasadded at a rate of 1 mL/min by means of a syringe pump. At thecompletion of the addition, the reactor contents were stirred at 100° C.for 4 hours. The reactor was sampled to obtain an aliquot of the 7.0mole ethoxylate of 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol. Higherethoxylates were prepared by adding sufficient ethylene oxide to preparethe 15, 17, and 25 mole ethoxylates of2,5,8,11-tetramethyl-6-dodecyne-5,8-diol. Samples of each ethoxylatewere removed from the reactor and characterized by matrix assistedlaser-desorption/ionization (MALD/I) analysis.

The surface tension y and foam data in Table 10 were obtained for 0.1 wt% aqueous solutions of these S-124 ethoxylates. Table 10 also shows theefficiency pC₂₀ data.

TABLE 10 Additional Total γ γ γ γ γ RM Foam Ex Moles EO EO pC₂₀ 0.1 b/s1 b/s 6 b/s 15 b/s 20 b/s Initial (t to 0) 54G 3.0 7.0 4.45 27.3 27.930.1 36.3 35.2 4.9 cm (>300 s) 54H 11.0 15.0 4.28 33.6 38.4 42.3 45.842.7 3.0 cm (>300 s) 54J 13.0 17.0 4.10 36.3 40.6 44.0 47.5 46.3 3.0 cm(>300 s) 54K 15.0 25.0 3.96 42.5 45.5 48.1 50.9 52.5 2.1 cm (>300 s)

EXAMPLE 55

Table 11 presents additional surface tension (γ), foam and efficiency(pC₂₀) data which had been generated for the S-104 and S-124ethoxylate/propoxylates shown in Table 7.

TABLE 11 RM Foam R EO γ γ γ γ γ (cm) Base or EO PO & 0.1 1 6 15 20Initial Ex Diol B Moles Moles PO pC₂₀ b/s b/s b/s b/s b/s (t to 0) 39S-104 R 5 10 15 4.50 33.4 33.7 39.9 46.1 48.2 0.5 (1 s) 40 S-104 B 5 1015 4.58 34.3 37.2 40.5 43.1 45.7 0.5 (10 s) 41 S-104 R 15 2 17 4.20 32.336.0 43.8 49.0 50.7 4.5 (>300 s) 42 S-104 B 15 2 17 5.04 30.4 36.8 42.947.5 49.5 5.3 (>300 s) 43 S-104 R 15 10 25 4.42 31.0 33.8 44.5 48.3 52.82.8 (>300 s) 44 S-104 B 15 10 25 4.35 30.7 35.5 45.6 52.0 54.9 4.0 (>300s) 45 S-124 R 5 2 7 4.39 27.2 28.2 33.5 42.5 45.4 2.4 cm (0.2 cm) 46S-124 B 5 2 7 4.42 27.4 28.5 32.5 37.7 37.2 3.0 cm (0.3 cm) 47 S-124 R 510 15 4.57 30.8 31.8 40.8 52.8 55.1 1.8 cm (>300 s) 48 S-124 B 5 10 154.56 32.1 33.4 40.3 51.6 55.4 1.4 cm (>300 s) 49 S-124 R 15 2 17 4.3628.0 30.5 40.8 47.5 50.2 2.6 cm (>300 s) 50 S-124 B 15 2 17 4.17 28.631.1 42.5 47.4 50.0 2.5 cm (>300 s) 51 S-124 R 15 10 25 4.58 30.1 32.843.2 46.7 45.5 2.0 cm (>300 s) 52 S-124 B 15 10 25 4.55 29.9 33.7 41.446.9 48.8 4.8 cm (>300 s)

In sum, the ability of a surfactant to reduce surface tension under bothequilibrium and dynamic conditions is of great importance in theperformance of waterbased coatings, inks, adhesives, fountain solutionsand agricultural formulations. Low dynamic surface tension results inenhanced wetting and spreading under the dynamic conditions ofapplication, resulting in more efficient use of the formulations andfewer defects. Foam control is also an important attribute in manyapplications.

The family of surfactants disclosed in this invention provide an abilityto control foam while providing excellent dynamic surface tensionreduction. They will therefore have utility in applications such ascoatings, inks, adhesives, fountain solutions, agriculturalformulations, soaps and detergents.

Statement of Industrial Application

The invention provides compositions suitable for reducing theequilibrium and dynamic surface tension in water-based coating, ink,fountain solution and agricultural compositions.

1. A method for making an acetylenic diol ethylene oxide/propylene oxideadduct which is capped with two propylene oxide units which comprisesreacting an acetylenic diol ethylene oxide adduct with propylene oxidein the presence of a catalytically effective amount of a trialkylamine,the acetylenic diol moiety derived from2,4,7,9-tetramethyl-5-decyne-4,7-diol or2,5,8,11-tetramethyl-6-dodecyne-5,8-diol.
 2. The method of claim 1 inwhich the resulting adduct has the structure:

where r and t are 1 or 2, (n+m) is 1.3 to 30 and p and q are each
 1. 3.The method of claim 1 in which the trialkylamine is trimethylamine. 4.The method of claim 2 in which (n+m) is 1.3 to
 15. 5. The method ofclaim 2 in which (n+m) is 1.3 to
 10. 6. The method of claim 2 in whichthe acetylenic diol moiety is derived from2,4,7,9-tetramethyl-5-decyne-4,7-diol.
 7. The method of claim 2 in whichthe acetylenic diol moiety is derived from2,5,8,11-tetramethyl-6-dodecyne-5,8-diol.
 8. The method of claim 6 inwhich (n+m) is 1.3 to
 10. 9. The method of claim 7 in which (n+m) is 1.3to
 10. 10. The method of claim 1 in which the temperature of thereaction is 40-150° C., the pressure is 2-20 bar and the trialkylamineis present at 0.001 to 10 wt % of the total reactant mass.
 11. Anacetylenic diol ethylene oxide/propylene oxide adduct of the structure:

where r and t are 1 or 2, (n+m) is 1.3 to 30 and (p+q) is 1 to 10, theethylene oxide and propylene oxide units being distributed along thealkylene oxide chain in blocks or randomly.
 12. An acetylenic diolethylene oxide/propylene oxide adduct of the structure:

where r and t are 1 or 2, (n+m) is 1.3 to 30 and (p+q) is 1 to 10, theethylene oxide and propylene oxide units being distributed along thealkylene oxide chain in blocks.
 13. The acetylenic diol ethyleneoxide/propylene oxide adduct of claim 12 in which the adduct is cappedwith the propylene oxide units.
 14. The acetylenic diol ethyleneoxide/propylene oxide adduct of claim 13 in which (n+m) is 1.3 to 15.15. The acetylenic diol ethylene oxide/propylene oxide adduct of claim13 in which (n+m) is 1.3 to 10 and (p+q) is 1 to
 3. 16. The acetylenicdiol ethylene oxide/propylene oxide adduct of claim 13 in which theacetylenic diol moiety is derived from2,4,7,9-tetramethyl-5-decyne-4,7-diol.
 17. The acetylenic diol ethyleneoxide/propylene oxide adduct of claim 13 in which the acetylenic diolmoiety is derived from 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol.
 18. Theacetylenic diol ethylene oxide/propylene oxide adduct of claim 16 inwhich (n+m) is 1.3 to 10 and (p+q) is 1 to
 3. 19. The acetylenic diolethylene oxide/propylene oxide adduct of claim 17 in which (n+m) is 1.3to 10 and (p+q) is 1 to
 3. 20. The acetylenic diol ethyleneoxide/propylene oxide adduct of claim 18 in which (p+q) is
 2. 21. Theacetylenic diol ethylene oxide/propylene oxide adduct of claim 19 inwhich (p+q) is
 2. 22. The acetylenic diol ethylene oxide/propylene oxideadduct of claim 20 which is the 5 mole ethoxylate/2 mole propoxylateadduct of 2,4,7,9-tetramethyl-5-decyne-4,7-diol.